Adsorptive separations using zeolitic structures as adsorbents are well known in the prior art for resolving a multitude of gas mixtures. Such separations are predicated upon the compositions of the gas mixtures and the components' selectivity for adsorption on adsorbents, such as zeolites.
The use of nitrogen in industrial gas applications has seen significant growth particularly with the development of non-cryogenic gas mixture separations. A major field of nitrogen separation comprises the separation of nitrogen from air. The removal of nitrogen from air results in an enriched oxygen gas component which is less strongly adsorbed by appropriate zeolites which are selective for nitrogen adsorption. When oxygen is desired as product typically at elevated pressure, it is desirable to adsorb nitrogen from air to result in unadsorbed oxygen enriched product passing over a nitrogen selective adsorbent. The nitrogen is then removed during a stage of desorption, typically at lower pressure. This results in oxygen being recovered at the pressure of the feed air, while nitrogen is recovered at a pressure below the feed air pressure. As a result, for the production of oxygen without significant pressure loss in an adsorptive separation of air, it is desirable to utilize nitrogen selective adsorbents such as the family of zeolites.
Although various zeolites are naturally occurring and various synthetic zeolites are known, some of which have appropriate selectivities for nitrogen over oxygen and other less strongly adsorbed substances such as hydrogen, argon, helium and neon, the industry has attempted to enhance the performance of various zeolites to improve their selectivity and capacity for nitrogen over such less strongly adsorbed substances such as oxygen. For instance, in U.S. Pat. No. 4,481,018, various polyvalent cation (particularly alkaline earth elements magnesium, calcium, strontium and barium) X-zeolites and faujasites are known which have low silicon to aluminum ratios in the order of approximately 1 to 1.2. The zeolites of this patent have utility for nitrogen adsorption, particularly from gas mixtures such as air when activated in a particular technique which minimizes the presence of water as it evolves from the material. The technique is further described in U.S. Pat. No. 4,544,378.
In U.K. Patent 1,580,928, a process for making low silica X-zeolites ("LSX"; where LSX is X-zeolite with a Si/Al=1 in the reference) is set forth comprising preparing an aqueous mixture of sources of sodium, potassium, aluminate and silicate and crystallizing the mixture at below 50.degree. C. or aging the mixture at 50.degree. C. or below followed by crystallizing the same at a temperature in the range of 60.degree. C. to 100.degree. C.
Gunter H. Kuhl in an article "Crystallization of Low-Silica Faujasite" appearing in Zeolites (1987) 7, p451 disclosed a process for making low silica X-zeolites comprising dissolving sodium aluminate in water with the addition of NaOH and KOH. Sodium silicate was diluted with the remaining water and rapidly added to the NaAlO.sub.2 -NaOH-KOH solution. The gelled mixture was then aged in a sealed plastic jar for a specified time at a specified temperature. The product was filtered and washed.
Other low silica X-zeolite synthesis processes are available, such as those set forth in U.S. Pat. No. 4,606,899.
In U.S. Pat. No. 3,140,931, the use of crystalline zeolitic molecular sieve material having apparent pore sizes of at least 4.6 Angstroms for separating oxygen-nitrogen mixtures at subambient temperatures is disclosed.
U.S. Pat. No. 3,140,932 specifically claims Sr, Ba, or Ni ion exchanged forms of zeolite X.
U.S. Pat. No. 3,313,091 claims the use of Sr X-zeolite at adsorption temperatures near atmospheric, and subatmospheric desorption pressures.
It is also known in U.S. Pat. No. 4,557,736 to modify X-zeolites by ion exchange of available ion sites with several divalent cations to produce a binary ion exchanged X-zeolite wherein the binary ions which are exchanged comprise calcium and strontium. These binary ion exchanged X-zeolites using calcium and strontium are reported to have higher nitrogen adsorption capacity, low heat of nitrogen adsorption and good nitrogen selectivity for air separation.
It is also known to exchange X-zeolites with lithium to provide an improved nitrogen selective adsorbent as set forth in U.S. Pat. No. 4,859,217. This patent suggests an improved nitrogen adsorbent can be achieved when an X-zeolite is exchanged with lithium cations at greater than 88%. The starting material for this patented zeolite is sodium X-zeolite. Therefore, the patent recites a lithium-sodium X-zeolite for nitrogen adsorption.
The prior art lithium X-zeolite was reported in U.S. Pat. No. 3,140,933 as useful for nitrogen-oxygen separations.
U.S. Pat. No. 2,882,244 discloses the direct synthesis and ion exchange of zinc X-zeolite from sodium X-zeolite using zinc nitrate. Exchange levels from 47-100% are reported.
Multiple cation exchange of zeolites with alkaline earth metals is disclosed in U.S. Pat. Nos. 4,964,889; 5,152,813 and 5,174,979.
East German Patent 150,886 discloses zinc A-zeolites or alkaline earth, zinc A-zeolites and specifically exemplifies NaZn(20)A-zeolite for selective adsorption of propene.
East German Patent 150,889 describes 5A-zeolites highly exchanged with zinc as being economically disadvantageous. NaZn(20)A-zeolite is mentioned. The claims include Li(5-30%)Zn(10-25%)A-zeolite for separation of ethene and propene from gas mixtures.
In an article by R. Schollner, et al., "Studies on the Determination of Cation Positions in Zeolites of the Faujasite Type III. Positions and Influence of Li Cations on Diffusion of Butene Isomers in 4A and 5A Zeolites", appearing in Z.phys.Chemie, 263,1 (1982), 97-110, the production of NaZnA-zeolite is mentioned, and the interaction of lithium and divalent cations on olefin adsorption is disclosed.
In an article entitled, "Investigations of the Arrangement and Mobility of Li ions in X- and Y-zeolites and the Influence of Mono- and Divalent Cations on It" by H. Herden, W. D. Einicke, R. Schollner and A. Dyer, appearing in J. Inorganic Nuclear Chemistry, Vol. 43, No. 10, pages 2533 thru 2536 (1981), the existence of mixed cation, sodium, lithium (55%) and zinc (8%) exchanged X-zeolites are set forth with a Si/Al ratio of 1.35. Physical parameters of the exchange zeolites are discussed with a general recitation to adsorptive and catalytic utilities of zeolites in general.
In an article entitled, "Arrangement and Mobility of Li ions in X- and Y-zeolites" by H. Herden, G. Korner and R. Schollner, appearing in J. Inorganic Nuclear Chemistry, Vol. 42, pages 132-133 (1979), a comparable disclosure of mixed cation, lithium and calcium, barium and zinc exchanged X-zeolites are set forth.
Asahi Chemical Industry Co., Ltd., in a series of Japanese patent publications, describes the use of cation exchanged X- and A-zeolites for various organic and chemical separations. Cations include lithium, magnesium, calcium, strontium, zinc, cadmium, copper, cobalt, manganese, and ammonium. Silicon to aluminum ratios are recited to be no greater than 4.5, or silica to alumina ratios no greater than 8.5. See Japanese 58-13527; 55-55123; 54-19920; and 53-111015.
Japanese Patent Publication 48-41439 discloses similar cation exchanges for A-zeolites used to refine monosilane.
Although improved exchanged X-zeolite adsorbents have been reported in the art for nitrogen adsorptions, and particularly the high performance of highly lithium exchange X-zeolites are known, such zeolites are difficult to achieve at high level lithium exchange and constitute an expensive adsorbent to produce for nitrogen separations. Such production difficulties and expense limit the use of such exchanged X-zeolites to produce either nitrogen or oxygen in competition with other separation technologies, such as cryogenic distillation and membrane separations. Therefore, a problem exists in the art for providing an appropriately exchanged X-zeolite for effective nitrogen adsorptive separation using an exchanged X-zeolite which is readily produced and has a favorable cost so as to result in competitively priced nitrogen, oxygen or other gas component product pricing. The art also desires to have a high selectivity exchanged X-zeolite with reasonable working capacities which do not inhibit continuous operation or adsorbent regeneration. These unresolved problems are achieved by the present invention, which is set forth below.